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THERMODYNAMIC PROPERTY RELATIONS

Determining unknown thermodynamic properties from limited available data Properties such as temperature, pressure, volume, and mass can be measured directly Properties such as internal energy, enthalpy, and entropy are not so easy to determine (they cannot be measured directly or related to easily measurable properties through some simple relations) It is essential that we develop some fundamental relations between commonly encountered thermodynamic properties and express the properties that cannot be measured directly in terms of easily measurable properties

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We make use of state postulate Mathematically: z = z(x,y) where x and y are the two independent properties that fix the state and z represents any other property Recall: The variation of z(x, y) with x when y is held constant is called the partial derivative of z with respect to x, and it is expressed as:

Total differential:

total differential change in z(x, y) for simultaneous changes in x and y

This is an important relation for partial derivatives, and it is used in calculus to test whether a differential dz is exact or inexact

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Reciprocity Relation

Cyclic Relation

THE MAXWELL RELATIONS

The equations that relate the partial derivatives of properties P, v, T, and s of a simple compressible system to each other are called the Maxwell relations Recall Gibbs relations:

Consider: Helmholtz function (a)

Gibbs function (g)

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Additional Gibbs relations

Comparing with:

Maxwell Relations

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THE CLAPEYRON EQUATION

Derived from Maxwells relations Enables to determine the enthalpy change associated with a phase change (hfg) from a knowledge of P, v, and T data alone Consider:

For phase change: Psat=f(Tsat)

For an isothermal liquidvapour phase-change process, the integration yields:

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Advantage of Clapeyron Equation?

The Clapeyron equation is applicable to any phase-change process that occurs at constant temperature and pressure

Approximations: If vg >> vf (at low P)

If

ClapeyronClausius equation

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General Relations for du, dh, ds, cv, and cp

Internal Energy Change Let: u = u(T, v)

Let: s = s(T, v)
Substituting the above relation in the Tds relation,

Rewriting,

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The change in internal energy of a simple compressible system associated with a change of state from (T1, v1) to (T2, v2) is determined by integration:

Enthalpy change:
h = h(T, P)

s = s(T, P)

Substituting the above relation in the Tds relation,

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The change in enthalpy of a simple compressible system associated with a change of state from (T1, P1) to (T2, P2) is determined by integration:

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Entropy change

Specific heats

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Defining volume expansivity and the isothermal compressibility , which are defined as:

Mayer relation

Inferences:

The difference between cp and cv approaches zero as the absolute temperature approaches zero The difference between the two specific heats is very small and is usually disregarded for substances that are nearly incompressible, such as liquids and solids

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THE JOULE-THOMSON COEFFICIENT

The temperature behavior of a fluid during a throttling process is described by the JouleThomson coefficient, defined as

Joule-Thomson coefficient represents the slope of constant h lines on a T-P diagram

Cooling effect cannot be achieved by throttling unless the fluid is below its maximum inversion temperature

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